Rearrangement Reaction Based on the Structure of N-Fluoro- N-alkyl Benzenesulfonamide

Article abstract of DOI:10.1021/acs.joc.8b01841

A novel rearrangement reaction based on the structure of N-fluoro-N-alkyl benzenesulfonamide was developed. The reaction proceeded readily at 50 °C in formic acid and generated a variety of benzenesulfonamides and aldehydes or ketones simultaneously. The reaction mechanism is believed to be a concerted mechanism that consist of 1,2-aryl migration with the departure of fluorine anion via an S_N2 mechanism. This rearrangement reaction features an interesting reaction mechanism, mild reaction conditions, simple operations, and a broad substrate scope.

Full text of DOI:10.1021/acs.joc.8b01841

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Article
A Rearrangement Reaction based on the
Structure of N-fluoro-N-alkyl Benzenesulfonamide
Han-Ying Wang, Xiao-Qiu Pu, and Xian-Jin Yang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01841 • Publication Date (Web): 27 Sep 2018
Downloaded from http://pubs.acs.org on September 27, 2018
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A Rearrangement Reaction Based on the Structure of
N-fluoro-N-alkyl Benzenesulfonamide
a†
b†
a, b
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HanꢀYing Wang, XiaoꢀQiu Pu and XianꢀJin Yang *
a.
Key Lab for Advanced Material & Institute of Fine Chemicals, East China University of Science and Technology,
1
b.
30 Meilong Road, Shanghai 200231, China. Eꢀmail: yxj@ecust.edu.cn
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 345 Lingling Road, Shanghai 200032, China.
†
These authors contributed equally to this work.
ABSTRACT： A novel rearrangement reaction based on the structure of NꢀfluoroꢀNꢀalkyl benzenesulfonamide was
developed. The reaction proceeded readily at 50°C in formic acid and generated a variety of benzenesulfonamides
and aldehydes or ketones simultaneously. The reaction mechanism is believed to be a concerted mechanism that
N
consist of 1,2ꢀaryl migration with the departure of fluorine anion via an S 2 mechanism. This rearrangement
reaction features an interesting reaction mechanism, mild reaction conditions, simple operation, and a broad
substrate scope.
INTRODUCTION:
The Beckmann rearrangement (BKR) is an important method in organic synthesis for preparing Nꢀsubstituted
1
amides from ketoximes. The conventional BKR is catalyzed by strong Brønsted or Lewis acids, such as
2
concentrated sulfuric acid, PCl
5
in diethyl ether, and hydrogen chloride in acetic anhydride. The concerted or
3
4
stepwise nature of the BKR mechanism is of theoretical interest. However, until now, few studies about BKR
involve fluoronitrogens have been reported.
5
NꢀF compounds usually serve as electrophilic fluorinating agents, such as Selectfluor and
6
Nꢀfluorobenzenesulfonimide. In recent years, a wide variety of NꢀF compounds have been developed as fluorine
7
sources due to their potential radical fluorination ability. Unlike previous studies, the NꢀF compounds were utilized
as substrates for a rearrangement in this study, which is similar to the BKR, undergoing the departure of one group
and the 1,2 migration of another group.
Most rearrangement reactions are migrations from an atom to an adjacent one (called 1,2ꢀshifts), but some occur
8
over longer distances. Migrations from a carbon to a nitrogen atom are used to prepare amines from acid derivatives
9
ꢀ10
(Scheme 1c) or ketones (Scheme 1a,b).
were generated for this reaction.
Traditional reactions usually afford one product, whereas two products
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Our group recently introduced
a new method to synthesize NꢀfluoroꢀNꢀalkylbenzenesulfonamides.
Unexpectedly, this kind of compound decomposed to benzenesulfonamide (yield 45%) and aldehyde simultaneously
in dichloromethane (DCM) overnight (Scheme 2). Inspired by this discovery, we investigated the function of the NꢀF
bond in this rearrangement and detected the detailed mechanistic interactions.
RESULTS AND DISCUSSION:
To determine the optimized conditions, Nꢀ(2ꢀchloroꢀ1ꢀphenylethyl)ꢀNꢀfluoroꢀ4ꢀmethoxybenzenesulfonamide (1)
was synthesized first as the model substrate to screen the conditions for this reaction. Experiments (Table 1) revealed
that the reaction solvent exerted a significant influence on the outcome, and the use of methanol, ethanol, or benzyl
alcohol as solvents resulted in no desired product formation [see Supporting Information (SI)]. It was observed that
formic acid was the optimal choice (entries 1–8). Notably, the reaction barely progressed without water in the
solvent (entries 9–11). However, the yield did not improve when water content in the solvent was optimized (entry
1
2). Increasing the temperature to 50°C led to an improved yield of 97% as well as a shorter reaction time (1 hour),
but an even higher temperature reduced the yield (entries 13–15).
Table 1 Optimization of the reaction conditions.
[a]
Entry
Solvent
CH CN
T (°C)
Time (h)
Yield (%)
1
2
3
r.t.
r.t.
24
24
23
35
Toluene
THF
3
4
5
6
r.t
r.t.
r.t.
r.t.
24
24
24
24
26
Acetone
EtOAc
4
3
0
6
CH Cl
2 2
50
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1.4-dioxane
HCOOH
r.t.
r.t
r.t
24
24
24
19
76
nd
13
50
64
97
88
60
[b,c]
CH Cl
2 2
[b]
2
1
0
1
2
3
4
5
CH
2
Cl
r.t.
r.t.
24
24
24
1
[c]
1
1
1
1
1
CH Cl
2 2
CH Cl :H O=10:1
2
2
2
r.t.
HCOOH
HCOOH
HCOOH
50
1
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70
0.5
0.5
reflux
[
a] Isolated yield after column chromatography. [b] The solvent was dried by
refluxing with CaH . [c] The reaction was performed under an N atmosphere.
2
2
With the optimized conditions in hand, a library of NꢀfluoroꢀNꢀalkyl benzenesulfonamides was synthesized with
structural and electronic modifications to examine the substrate scope and functional group tolerance of the reaction.
The substrates were synthesized in two main ways: [a] by directly adding alkenes to
12
NꢀchloroꢀNꢀfluorobenzenesulfonamide and [b] the Mitsunobu reaction between benzyl alcohol and Nꢀfluoro
benzenesulfonamide (Scheme 3).
First, the aryl substituent in styrene or benzyl alcohol was varied, and the data were summarized. As shown in
Table 2, the paraꢀsubstituted aryls bearing electronꢀdonating, such as alkyl and alkoxyl groups, effectively yielded
3
the corresponding products 2a–2d, while the aryl bearing strong electronꢀwithdrawing group CF failed to afford the
arrangement product 2e. Interestingly, changing the R group to a halogen (bromine) had no significant effect on
yield. In addition, meta-methyl and orthoꢀsubstituent aryls also exhibited good reactivities to give the desired
products 2f–2h in moderate to good yields. Substrate with diꢀsubstitutents on the aryl ring was also compatible to
give product 2i with a considerable yield. Furthermore, substrates with thienyl and naphthyl rings also afforded the
corresponding products 2j and 2k at 60% and 96% yields, respectively.
Next, the scope of the Nꢀfluoro benzenesulfonamide was explored (Table 2). Again, the paraꢀsubstituted aryls
effectively produced the target products 2l–2p with excellent yields.
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Table 2 Scope of N-fluoro-N-alkyl benzenesulfonamides.
0
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[
a]
Reactions were performed using 0.25 mmol of substrates in 2 mL of formic acid
a
b
c
d
at 50°C for 1–6 h. Isolated yields are given. R = Cl. R = Br. R = H. At room
temperature.
Because of the volatility of the aliphatic aldehydes in our reactions, the other product was difficult to isolate and
purify. Therefore, some substrates with special skeletons were tested to afford the alphaꢀchlorocyclohexanone 2r
and the corresponding ringꢀopening product 2q, whose structure contained aromatic amine and carbonyl groups
(Scheme 4). The compound 1s was anticipated to provide the ringꢀopening product. Nevertheless, it was converted
to 1ꢀindanone 2s, which may have been due to high ring strain.
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A variety of control experiments were carried out to gain mechanistic insight. At first, compounds 1t and 1u
failed to react under our standard conditions (Scheme 5a) and the importance of the fluorine atom in this reaction
was confirmed. Then the inapplicability of compounds 1v and 1w (Scheme 5b) indicated that only aryl migration
was feasible. The experiment (Scheme 5c) showed that when there was no substituent on the alpha carbon, an
aromatic aldehyde was generated instead of the rearrangement product. This observation probably suggested an S
mechanism, which would be discussed in later section. In the presence of radical inhibitors
,2,6,6ꢀtetramethylpiperidine 1ꢀoxyl (TEMPO), the compound 1a gave 2a in 87% yield (Scheme 5d). Moreover,
N
2
a
2
when the radical trap 1,1ꢀdiphenylethylene was subjected to the standard reaction conditions, the targeted product 2a
were identified with 89% yield (Scheme 5d), which indicated that the rearrangement may not go through a radical
process.
The proposed mechanism of this reaction is shown in Scheme 6. Since the arylsulfonyl group destabilizes alpha
nitrenium cation (Path A), the concerted mechanism (Path B) is much more reasonable in this work. The formic
acid promoted the departure of fluorine anion and the betaꢀaryl group carrying a pair of electrons migrated to the
electronꢀdeficient nitrogen atom synchronously to generate the intermediate A. Then the water was proposed to be
served as an nucleophile attacking the carbonium ions to generate the intermediate B. The intermediate B would
further decompose into the product 2a and C by hydrolysis. This concerted mechanism is also consistent with the
result of the substrate 1x. By comparison, the benzene ring and the fluorine atom of compound 1x are in the same
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plane, so the backside route of attack was hindered and the 1,2ꢀhydrogen shift occurred. This difference of two
substrates might provide some evidence for the proposed S 2 mechanism.
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CONCLUSION:
In summary, we developed a novel rearrangement reaction based on the structure of
NꢀfluoroꢀNꢀalkyl
benzenesulfonamide, which generated benzene sulfonamide in situ and aldehyde or ketone. The concerted
reaction mechanism is believed to consist of an aryl or hydrogen migration with expulsion of the fluorine
anion via an S 2 mechanism. This finding will allow us to further develop the organic reactions in which the
N
NꢀF bond participates. Further studies are underway in our laboratory.
EXPERIMENTAL SECTION:
General Considerations. Unless otherwise noted, all commercially available compounds were purchased
without further purification. Dry THF was obtained by refluxing with Na. Flash column chromatography
was carried out on silica gel (300ꢀ400 mesh). Thin layer chromatography (TLC) was performed using silica
gel HSGF 254 plates and visualized by UV light (254nm). NMR spectra were recorded on a Brucker
1
19
13
AMꢀ400 (400 MHz for H; 376 MHz for F; 100MHz for C) spectrometer. IR spectra were recorded on a
Bruker TENSOR 27 FTIR Spectrometer equipped with a Platinum ATR detector. LRMS and HRMS Mass
Spectra were recorded on a Waters GCT Premier mass spectrometer with electron impact (70eV). Chemical
shifts are given in parts per million (ppm) using residual solvent signals as internal standard (CHCl , δ =
3
1
13
7
.26 ppm or DMSOꢀ 6
d
, δ = 2.50 ppm for H NMR, δ = 77.16 ppm or DMSOꢀd6, δ = 39.52 ppm for
C
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NMR). HRMS (EI) Mass Spectra were recorded on a Waters GCT Premier ms spectrometer with electron
impact.
General Procedures. To a round bottom flask equipped with a magnetic stir bar,
NꢀfluoroꢀNꢀalkyl
benzenesulfonamide (1.0 equiv.) was dissolved as well as possible in methanoic acid (0.2 M). The
1
reaction was allowed to stir at 50 °C and was monitored by TLC (Thin Layer Chromatography). Then the
mixture was purified via silica gel chromatography (eluent: petroleum ether/ethyl acetate, 20:1) to afford the
products 2aꢀ2x. The isolated yields of the products 2aꢀ2x do not take into account residual solvents.
Preparation of Substrate N-Fluoro-N-alkyl benzenesulfonamide. Method A: To a solution of the styrene (1.0
equiv.) in DCM (0.5 M), CFBSA (1.2 equiv.) was added dropwise. Then the mixture stirred at room temperature for
12 hours. The solvent was then removed under reduced pressure and the residue was purified by flash
chromatography on silica gel (eluent: petroleum ether/ethyl acetate, 60:1). Method B: To a solution of the CFBSA
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
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4
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5
5
5
6
0
1
2
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4
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6
7
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0
1
2
3
4
5
6
7
8
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0
1
2
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2
3
4
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2
3
4
5
6
7
8
9
0
(
1.0 equiv.) in DCM:MeCM = 3:1 (0.5 M), potassium bromide (1.5 equiv.) was added . Then the mixture stirred at
room temperature for 6 hours or until completion observed by TLC. The styrene (1.0 equiv.) was added. When the
reaction completed, the solvent was removed under reduced pressure and the residue was purified by flash
chromatography on silica gel (eluent: petroleum ether/ethyl acetate, 60:1). Method C: To a solution of the alcohol
(
3
1.0 equiv.), Nꢀfluorobenzenesulfonamide (1.2 equiv.) and PPh (1.2 equiv.) in dry THF (0.2 M), diisopropyl
azodicarboxylate (1.2 equiv.) was added dropwise at 0 °C. The reaction then stirred for 1ꢀ12 hour at room
temperature, or until completion observed by TLC. The solvent was then removed under reduced pressure and the
residue was purified by flash chromatography on silica gel (eluent: petroleum ether/ethyl acetate, 40:1). All yields
are not optimized.
b
N-(2-Bromo-1-phenylethyl)-N-fluorobenzenesulfonamide (1a ): White solid, 235.6 mg, yield 66%; m.p.:
1
9
6.2ꢀ98.1 °C; H NMR (400 MHz, CDCl ) δ: 7.97ꢀ7.91 (m, 2H), 7.79ꢀ7.73 (m, 1H), 7.89ꢀ7.66 (m, 2H), 7.41ꢀ7.30
3
13
(
3
m, 5H), 5.12 (t, J = 7.4 Hz, 1H), 3.99ꢀ3.95 (m, 1H), 3.88 (dd, J = 7.4, 1.0 Hz, 1H); C NMR (100 MHz, CDCl ) δ:
2
19
138.2, 135.4, 132.1, 130.0, 129.6, 129.3, 129.1, 127.9, 59.9 (d, JCꢀF = 11.8 Hz, 1C), 47.4; F NMR (376 MHz,
ꢀ1
CDCl
3
) δ: ꢀ71.59 (s, 1F). IR (KBr, cm ): 3067.4, 3021, 2981, 2852, 1603, 1522, 1511, 1423; HRMS (EIꢀTOF) m/z:
+
[
M ꢀ HF] Calcd for C14
H
12BrNO
2
S 336.9772; Found 336.9776.
c
1
N-Fluoro-N-(1-phenylethyl)benzenesulfonamide (1a ): White solid, 145.1 mg, yield 52%; m.p.: 40.1 °C; H
3
NMR (400 MHz, CDCl ) δ: 7.91ꢀ7.89 (m, 2H), 7.68ꢀ7.64 (m, 1H), 7.54ꢀ7.49 (m, 2H), 7.35ꢀ7.27 (m, 5H), 4.97 (dq, J
1
3
=
33.4, 6.8 Hz, 1H), 1.68 (dd, J = 6.9, 1.5 Hz, 3H); C NMR (100 MHz, CDCl ) δ: 138.9 (d, JCꢀF = 2.3 Hz, 1C),
3
2
3
19
1
34.8, 134.6, 129.6, 129.2, 128.6, 128.4, 127.7, 63.0 (d, JCꢀF = 13.0 Hz, 1C), 18.8 (d, JCꢀF = 9.1 Hz, 1C); F NMR
ꢀ
1
+
(
376 MHz, CDCl
3
) δ: ꢀ67.08 (s, 1F). IR (KBr, cm ): 3006.2, 2913.4, 2855.6; HRMS (EIꢀTOF) m/z: [M ꢀ HF] Calcd
for C H NO S 259.0667; Found 259.0665.
14 13
2
1
N-Fluoro-N-(1-(p-tolyl)ethyl)benzenesulfonamide (1b): White solid, 181.7 mg, yield 62%; m.p.: 42.1 °C; H
NMR (400 MHz, CDCl ) δ: 7.92ꢀ7.87 (m, 2H), 7.69ꢀ7.63 (m, 1H), 7.55ꢀ7.48 (m, 2H), 7.25ꢀ7.20 (m, 2H), 7.14ꢀ7.09
3
1
3
(
m, 2H), 2.33 (s, 1H), 4.95 (dq, J = 33.5, 6.8 Hz, 1H), 1.66 (dd, J = 6.9, 1.5 Hz, 3H); C NMR (100 MHz, CDCl
3
) δ:
2
1
38.2, 135.8 (d, JCꢀF = 2.6 Hz, 1C), 134.9, 134.5, 129.5, 129.3, 129.1, 127.7, 62.8 (d, JC-F = 13.0 Hz, 1C), 21.2, 18.8
3
19
ꢀ1
(d, J = 8.8 Hz, 1C); F NMR (376 MHz, CDCl ) δ: ꢀ67.29 (s, 1F). IR (KBr, cm ): 3098.1, 3073.4, 2945.1,
CꢀF
3
+
2
2
854.8; HRMS (EIꢀTOF) m/z: [M ꢀ HF] Calcd for C15H15NO S 273.0823; Found 273.0822.
N-(1-(4-(tert-Butyl)phenyl)-2-chloroethyl)-N-fluorobenzenesulfonamide (1c): White solid, 324.8 mg, yield
1
8
7
8%; m.p.: 84.7 °C; H NMR (400 MHz, CDCl
3
) δ: 7.80ꢀ7.78 (m, 2H), 7.61ꢀ7.56 (m, 1H), 7.44ꢀ7.39 (m, 2H),
.30ꢀ7.25 (m, 2H), 7.20ꢀ7.17 (m, 2H), 5.14 (dt, J = 39.3, 7.2 Hz, 1H), 4.17 (dd, J = 11.5, 7.2 Hz, 1H), 3.88 (dd, J =
13
11.5, 7.3 Hz, 1H), 1.31 (s, 9H); C NMR (100 MHz, CDCl ) δ: 152.4, 134.6, 134.5, 130.0, 129.5, 129.0, 128.8,
3
2
19
1
3
3
25.6, 68.0 (d, JCꢀF = 11.5 Hz, 1C), 43.6, 34.7, 31.4; F NMR (376 MHz, CDCl
3
) δ: ꢀ74.14 (s, 1F). IR (KBr, cmꢀ1):
+
066.6, 1583.5, 1130.6, 898.3, 687.3; HRMS (EIꢀTOF) m/z: [M ꢀ HF] Calcd for C18
49.0906.
H
20ClNO S 349.0903; Found
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N-(2-Chloro-1-(4-methoxyphenyl)ethyl)-N-fluorobenzenesulfonamide (1d): White solid, 295.0 mg, yield 86%;
1
m.p.: 71.1 °C; H NMR (400 MHz, CDCl
3
) δ: 7.80(d, J = 7.6 Hz, 2H), 7.62 (t, J = 7.6 Hz, 1H), 7.48ꢀ7.44 (m, 2H),
7
.21(d, J = 8.4 Hz, 2H), 6.82ꢀ6.79 (m, 2H), 5.08 (dt, J = 7.2 Hz, 39.2Hz, 1H), 4.15ꢀ4.10 (m, 1H), 3.88ꢀ3.83 (m,1H),
13
13
3
.80 (s, 3H); C NMR (100 MHz, CDCl
3
) δ: C NMR (100MHz, CDCl3) :160.4, 134.8, 134.6, 130.4, 129.5, 129.2,
2
3
19
1
25.2 (d, JC-F = 4.7 Hz, 2C), 114.1, 67.7 (d, J = 11.6 Hz, 1C), 55.6, 43.7 (d, J = 5.4 Hz, 1C); F NMR (376
C-F
C-F
ꢀ
1
+
MHz, CDCl
3
) δ: ꢀ72.10 (s, 1F). IR (KBr, cm ): 3056.4, 2961.3, 2923.2, 2838.6; HRMS (EIꢀTOF) m/z: [M ꢀ HF]
14ClNO S 323.0383; Found 323.0385.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
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3
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5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Calcd for C15
H
3
N-Fluoro-N-(1-(4-(trifluoromethyl)phenyl)ethyl)benzenesulfonamide (1e): Colorless oil, 156.2 mg, yield 45%;
1
3
H NMR (400 MHz, CDCl ) δ: 7.90ꢀ7.87 (m, 2H), 7.70ꢀ7.65 (m, 2H), 7.57ꢀ7.50 (m, 4H), 7.46ꢀ7.43 (m, 2H), 5.04
13
(dq, J = 33.1, 6.9 Hz, 1H), 1.68 (dd, J = 6.9, 1.3 Hz, 3H); C NMR (101 MHz, CDCl ) δ: 142.71, 134.85, 134.49,
3
2
1
30.56 (d, JC-F = 32.6 Hz), 129.54, 129.30, 128.08, 125.65 (q, JC-F = 3.8 Hz, 1C), 62.43 (d, JC-F = 13.0 Hz), 18.82 (d,
3
19
ꢀ1
J
C-F = 9.0 Hz, 1C); F NMR (376 MHz, CDCl
3
) δ: ꢀ62.68 (s, 3F), ꢀ67.25 (s, 1F). IR (KBr, cm ): 3252.2, 3248.3,
+
2
3
918.2, 1511.8, 1362.7, 1132.5, 978.2, 753.2; HRMS (EIꢀTOF) m/z: M Calcd for C15
47.0609.
13 4 2
H F NO S 347.0603; Found
N-(1-([1,1'-Biphenyl]-2-yl)ethyl)-N-fluorobenzenesulfonamide (1f): White solid, 259.2 mg, yield 73%; m.p.:
1
7
9.5ꢀ80.3 °C; H NMR (400 MHz, CDCl
3
) δ: 7.79ꢀ7.74 (m, 2H), 7.66ꢀ7.00 (m, 2H), 7.49ꢀ7.30 (m, 7H), 7.28ꢀ7.20
1
3
(
m, 3H), 5.03 (dq, J = 26.7, 6.7 Hz, 1H), 1.56 (dd, J = 6.8, 1.7 Hz, 3H); C NMR (100 MHz, CDCl
3
) δ: 141.1, 140.4,
2
1
37.2 (d, JCꢀF = 2.0 Hz, 1C), 134.6, 133.9, 130.3, 129.5, 129.4, 129.1, 128.4, 127.9, 127.9, 127.5, 127.4, 59.5 (d, JCꢀF
3
19
ꢀ1
3
= 12.9 Hz, 1C), 19.5 (d, JCꢀF = 10.3 Hz, 1C); F NMR (376 MHz, CDCl ) δ: ꢀ61.88 (s, 1F). IR (KBr, cm ): 3150.5,
+
1
369.2, 1180.3, 745.3, 572.1; HRMS (EIꢀTOF) m/z: M Calcd for C H FNO S 355.1042; Found 355.1040.
20
18
2
1
N-(1-(2-Bromophenyl)ethyl)-N-fluorobenzenesulfonamide (1g): Yellow oil, 146.3 mg, yield 41%; H NMR (400
MHz, CDCl ) δ: 7.98ꢀ7.96 (m, 2H), 7.70ꢀ7.66 (m, 1H), 7.57ꢀ7.49 (m, 4H), 7.29ꢀ7.24 (m, 1H), 7.15ꢀ7.11 (m, 1H),
.48 (dq, J = 30.8, 6.8 Hz, 1H), 1.62 (dd, J = 6.8, 1.8 Hz, 3H); C NMR (100 MHz, CDCl
3
13
3
5
3
) δ: 138.6 (d, JC-F = 1.5
2
Hz, 1C), 134.8, 134.4, 133.1, 129.7, 129.7, 129.3, 128.9 (d, JC-F = 2.5 Hz, 1C), 127.9, 123.2, 61.8 (d, JC-F = 13.1 Hz,
3
19
ꢀ1
1
1
C), 17.9 (d, J = 10.7 Hz, 1C); F NMR (376 MHz, CDCl ) δ: ꢀ66.42 (s, 1F). IR (KBr, cm ): 3435.7, 3066.9,
C-F 3
+
448.4, 1365.9, 1179.5, 1084.7, 757.9, 561.9; HRMS (EIꢀTOF) m/z: M Calcd for C14
H
2
13BrFNO S 356.9834;
Found 356.9832.
1
N-Fluoro-N-(1-(m-tolyl)ethyl)benzenesulfonamide (1h): Colorless oil, 190.5 mg, yield 65%; H NMR (400 MHz,
CDCl
3
) δ: 7.92ꢀ7.88 (m, 2H), 7.69ꢀ7.63 ( m, 1H), 7.55ꢀ7.49 (m, 2H), 7.23ꢀ7.07 (m, 4H), 4.94 (dq, J = 33.5, 6.9 Hz,
13
1
1
1
H), 2.32 (s, 3H), 1.67 (dd, J = 6.9, 1.5 Hz, 3H); C NMR (100 MHz, CDCl ) δ: 138.7 (d, J = 2.2 Hz), 138.3,
3
C-F
2
3
34.8, 134.5, 129.5, 129.1, 129.1, 128.5, 128.4, 124.7, 63.1 (d, JC-F = 13.0 Hz, 1C), 21.5, 18.8 (d, JC-F = 9.2 Hz,
19
ꢀ1
C); F NMR (376 MHz, CDCl
3
) δ: ꢀ66.96 (s, 1F). IR (KBr, cm ): 3097.8, 2954.5, 2925.1, 2856.5; HRMS
+
(EIꢀTOF) m/z: M Calcd for C15
H16FNO
2
S 293.0886; Found 293.0887.
1
N-(1-(3,4-Dimethylphenyl)ethyl)-N-fluorobenzenesulfonamide (1i): Yellow oil, 224.2 mg, yield 73%; H NMR
(
400 MHz, CDCl ) δ: 7.91ꢀ7.86 (m, 2H), 7.68ꢀ7.62 (m, 1H), 7.54ꢀ7.48 (m, 2H), 7.10ꢀ7.04 (m, 3H), 4.91 (dq, J =
3
13
3
3
3.8, 6.9 Hz, 1H), 2.22 (d, J = 2.8 Hz, 6H), 1.66 (dd, J = 6.9, 1.5 Hz, 3H); C NMR (100 MHz, CDCl ) δ: 136.9,
2
136.8, 136.2 (d, JC-F = 2.4 Hz, 1C), 134.9, 134.4, 129.8, 129.5, 129.0, 129.0, 125.2, 63.0 (d, JC-F = 13.0 Hz, 1C),
3
19
ꢀ1
1
2
9.9, 19.6, 18.9 (d, JC-F = 8.9 Hz, 1C); F NMR (376 MHz, CDCl
3
) δ: ꢀ67.32 (s, 1F). IR (KBr, cm ): 3427.2,
+
940.122, 1448.9, 1364.2, 1177.3, 735.5, 606.0; HRMS (EIꢀTOF) m/z: M Calcd for C16
H18FNO
2
S 307.1042;
Found 307.1040.
1
N-Fluoro-N-(1-(thiophen-2-yl)ethyl)benzenesulfonamide (1j): Yellow oil, 116.8 mg, yield 41%; H NMR (400
MHz, CDCl
3
) δ: 7.92ꢀ7.87 (m, 2H), 7.67ꢀ7.61 (m, 1H), 7.53ꢀ7.47 (m, 2H), 7.22 (dd, J = 5.1, 1.3 Hz, 1H), 7.03ꢀ7.00
13
(
m, 1H), 6.93ꢀ6.88 (m, 1H), 5.46 (dq, J = 37.4, 6.9 Hz, 1H), 1.75 (dd, J = 6.9, 1.3 Hz, 3H); C NMR (100 MHz,
2
CDCl
3
) δ: 140.6 (d, JC-F = 2.5 Hz, 1C), 134.9, 134.6, 129.4, 129.1, 126.7, 126.5, 126.1, 58.4 (d, JC-F = 13.3 Hz, 1C),
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ꢀ1
19.6 (d, JC-F = 8.3 Hz, 1C); F NMR (376 MHz, CDCl
3
) δ: ꢀ72.65 (s, 1F). IR (KBr, cm ): 3069.9, 2992.3, 1663.5,
+
1
448.7, 1363.4, 1176.9, 1088.7, 905.3, 707.8, 551.6; HRMS (EIꢀTOF) m/z: M Calcd for C12
H12FNO
2
S
2
285.0293;
Found 285.0290.
N-Fluoro-N-(1-(naphthalen-2-yl)ethyl)benzenesulfonamide (1k): White solid, 213.9 mg, yield 65%; m.p.:
1
8
9.3ꢀ91.2 °C; H NMR (400 MHz, CDCl ) δ: 8.20ꢀ8.14 (m, 1H), 7.95ꢀ7.85 (m, 3H), 7.83ꢀ7.78 (m, 1H), 7.66ꢀ7.54
3
13
(m, 3H), 7.55ꢀ7.40 (m, 4H), 5.99 (dq, J = 33.6, 6.8 Hz, 1H), 1.87 (dd, J = 6.8, 1.3 Hz, 3H); C NMR (100 MHz,
CDCl ) δ: 135.0, 134.7, 134.3, 134.0, 130.91, 129.5, 129.2, 129.2, 129.2, 126.8, 125.9, 125.6, 125.5, 125.3, 122.9,
7.9 (d, JC-F = 13.8 Hz, 1C), 17.1 (d, JC-F = 11.4 Hz, 1C); F NMR (376 MHz, CDCl
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
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5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
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8
9
0
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7
8
9
0
1
2
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
2
3
19
5
3
) δ: ꢀ70.68 (s, 1F). IR (KBr,
ꢀ
1
+
cm ): 2967.7, 2913.2, 2822.5; HRMS (EIꢀTOF) m/z: M Calcd for C18H16FNO S 329.0886; Found 329.0884.
2
N-Fluoro-4-nitro-N-(1-phenylethyl)benzenesulfonamide (1l): White solid, 187.9 mg, yield 58%; m.p.: 96.7ꢀ97.6
1
°
C; H NMR (400 MHz, CDCl
3
) δ: 8.28ꢀ8.25 (m, 2H), 7.99 (m, 2H), 7.30ꢀ7.22 (m, 5H), 5.09 (dd, J = 37.5, 6.93 Hz,
13
1
1
1
H), 1.73 (dd, J = 6.93, 1.30 Hz, 3H); C NMR (100 MHz, CDCl
3
) δ: 151.0, 140.6, 137.7, 130.8, 128.8, 128.7,
2
3
19
28.0, 124.1, 63.4 (d, JC-F = 13.17 Hz, 1C), 19.0 (d, JC-F = 7.82 Hz, 1C); F NMR (376 MHz, CDCl
3
) δ: ꢀ70.58 (s,
ꢀ
1
F). IR (KBr, cm ): 3336.5, 3250.5, 2922.8, 1524.8, 1347.7, 1306.9, 1156.8, 982.9, 738.8; HRMS (EIꢀTOF) m/z:
+
M Calcd for C H FN O S 324.0580; Found 324.0582.
1
4
13
2
4
N-(2-Chloro-1-(4-methoxyphenyl)ethyl)-N-fluoro-4-nitrobenzenesulfonamide (1m): White solid, 380.3 mg,
1
yield 98%; m.p.: 99.3°C; H NMR (400 MHz, CDCl
3
) δ: 8.25ꢀ8.21 (m, 2H), 7.93ꢀ7.90 (m, 2H), 7.17ꢀ7.14 (m, 2H),
6
.78ꢀ6.73 (m, 2H), 5.15 (dt, J = 41.0, 7.4 Hz, 1H), 4.13 (dd, J = 11.6, 7.9 Hz, 1H), 3.80ꢀ3.86 (m, 1H), 3.76 (s, 3H);
1
3
2
3
C NMR (100 MHz, CDCl ) δ: 150.9, 140.3, 140.1, 130.7, 129.5, 129.4, 129.0, 129.0, 123.9, 68.4 (d, JC-F = 11.6
3
19
ꢀ1
Hz, 1C), 43.3 (d, J = 4.6 Hz, 1C), 21.3; F NMR (376 MHz, CDCl ) δ: ꢀ74.67 (s, 1F). IR (KBr, cm ): 3433.9,
C-F
3
+
3
3
4
066.8,2942.3,1473.3, 1046.6, 686.9; HRMS (EIꢀTOF) m/z: [M ꢀ HF] Calcd for C15
68.0236.
H
13ClN
2
O
5
S 368.0234; Found
1
-Chloro-N-fluoro-N-(1-phenylethyl)benzenesulfonamide (1n): White oil, 187.8 mg, yield 60%; H NMR (400
MHz, CDCl
3
) δ: 7.80ꢀ7.77 (m, 2H), 7.48ꢀ7.44 (m, 2H), 7.32ꢀ7.28 (m, 5H), 4.99 (dq, J = 34.9, 6.9 Hz, 1H), 1.69 (dd,
13
J = 6.9, 1.5 Hz, 3H); C NMR (100 MHz, CDCl ) δ: 141.48, 138.45 (d, J = 2.3 Hz, 1C), 138.4, 133.3, 130.9,
3
C-F
2
3
19
1
3
29.5, 128.7, 128.5, 127.8, 63.1 (d, JC-F = 12.9 Hz. 1C), 19.0 (d, JC-F = 8.7 Hz, 1C); F NMR (376 MHz, CDCl ) δ:
ꢀ
1
ꢀ
68.03 (s, 1F). IR (KBr, cm ): 3342.2, 3150.3, 2914.8, 1641.3, 1212.7, 1241.9, 1108.7, 875.3, 730.3; HRMS
+
(EIꢀTOF) m/z: M Calcd for C14
H13ClFNO
2
S 313.0340; Found 313.0338.
N-(1-(4-(tert-Butyl)phenyl)-2-chloroethyl)-4-chloro-N-fluorobenzenesulfonamide (1o): White solid, 382.9 mg,
1
yield 95%; m.p.: 69.3 °C; H NMR (400 MHz, CDCl ) δ: 8.16ꢀ8.11 (m, 2H), 7.88ꢀ7.83 (m, 2H), 7.22ꢀ7.16 (m, 2H),
3
7
.12ꢀ7.06 (m, 2H), 5.06ꢀ5.25 (m, 1H), 4.13 (dd, J = 11.7, 8.1 Hz, 1H), 3.81 (dd, J = 11.7, 6.6 Hz, 1H), 1.23 (s, 9H);
1
3
3
C NMR (100 MHz, CDCl ) δ: 153.2, 150.8, 140.3, 130.8, 129.3 (d, JC-F = 3.8 Hz, 2C), 128.8 (d, JC-F = 2.1 Hz, 2C),
2
3
19
125.7, 123.8, 68.6 (d, JC-F = 11.4 Hz, 1C), 43.4 (d, JC-F = 4.3 Hz, 1C), 34.7, 31.2; F NMR (376 MHz, CDCl
3
) δ:
ꢀ1
+
ꢀ
76.49 (s, 1F). IR (KBr, cm ): 3101.6, 3045.1, 2875.4, 2875.1, 2745.2; HRMS (EIꢀTOF) m/z: M Calcd for
C H C FNO S 403.0576; Found 403.0574.
1
8
20 l2
2
4
-Chloro-N-(2-chloro-1-(4-fluorophenyl)ethyl)-N-fluorobenzenesulfonamide (1p): White solid, 226.3 mg, yield
1
62%; m.p.: 59.5ꢀ60.5 °C; H NMR (400 MHz, CDCl
3
) δ: 7.75ꢀ7.70 (m, 2H), 7.46ꢀ7.44 (m, 2H), 7.32ꢀ7.28 (m, 2H),
1
3
7
.04ꢀ6.99 (m, 2H), 5.13 (dt, J = 37.8, 7.2 Hz, 1H), 4.13 (dd, J = 11.5, 6.9 Hz, 1H), 3.86 (dd, J = 11.4, 7.7 Hz, 1H); C
3
NMR (100 MHz, CDCl ) δ: 164.6, 162.1, 141.9, 133.1, 131.0 (dd, JC-F = 8.4, 1.8 Hz, 2C), 130.9, 129.6, 115.9 (d, JC-F
2
3
19
=
21.7 Hz, 2C), 67.3 (d, J = 11.6 Hz, 1C), 43.4 (d, J = 5.6 Hz, 1C); F NMR (376 MHz, CDCl ) δ: ꢀ71.80,
C-F
C-F
3
ꢀ
1
+
ꢀ
111.19. IR (KBr, cm ): 3263.3, 3100.2, 2966.7, 2905.5; HRMS (EIꢀTOF) m/z: M Calcd for C14
2 2 2
H11Cl F NO S
364.9856; Found 364.9853.
N-Fluoro-N-(6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-yl)benzenesulfonamide (1q): White solid, 146.8 mg,
1
yield 46%; m.p.: 86.8ꢀ88.1 °C; H NMR (400 MHz, CDCl
3
) δ: 8.00ꢀ7.96 (m, 2H), 7.76ꢀ7.70 (m, 1H), 7.64ꢀ7.58 (m,
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2H), 7.22ꢀ7.08 (m, 4H), 4.87 (d, J = 25.0 Hz, 1H), 3.20ꢀ3.05 (m, 1H), 2.76ꢀ2.65 (m, 1H), 2.20ꢀ2.00 (m, 2H),
13
1
.95ꢀ1.85 (m, 1H), 1.80ꢀ1.73 (m, 1H), 1.73ꢀ1.60 (m, 2H); C NMR (100 MHz, CDCl
3
) δ: 138.3, 134.8, 134.5, 132.4
2
(
d, JC-F = 10.7 Hz, 1C), 130.1, 129.7, 129.3, 128.6 (d, JC-F = 12.5 Hz, 1C), 128.2, 126.2, 67.6, 35.7, 31.2 (d, JC-F
=
1
9
ꢀ1
8
1
.6 Hz, 1C), 27.5, 27.1; F NMR (376 MHz, CDCl
3
) δ: ꢀ52.70 (s, 1F). IR (KBr, cm ): 2941.2, 2916.0, 2849.9,
+
447.9, 1373.5, 1356.8, 1170.2, 1090.3, 895.0, 753.6, 681.1, 619.8, 565.5; HRMS (EIꢀTOF) m/z: M Calcd for
C
17
H18FNO
2
S 319.1042; Found 319.1044.
N-(2-Chloro-1-phenylcyclohexyl)-N-fluorobenzenesulfonamide (1r): Colorless oil, 242.2 mg, yield 66%; H
NMR (400 MHz, CDCl ) δ: 7.60ꢀ7.46 (m, 3H), 7.40ꢀ7.25 (m, 4H), 7.24ꢀ7.11 (m, 3H), 5.19ꢀ5.13 (m, 1H), 3.08 (d, J
13.9 Hz, 1H), 2.40ꢀ2.56 (m, 2H), 1.90ꢀ2.14 (m, 3H), 1.77 (dd, J = 47.2, 13.5 Hz, 2H); C NMR (100 MHz,
CDCl ) δ: 136.6, 136.0, 133.9, 129.0 (d, J = 1.1 Hz, 2C), 128.8, 128.7, 128.1, 127.2 (d, JC-F = 1.9 Hz, 2C), 72.4,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
3
13
=
3
C-F
2
19
7
3
2.3, 61.8, 61.7, 29.5, 28.9 (d, JC-F = 6.9 Hz, 1C), 21.1, 19.0; F NMR (376 MHz, CDCl ) δ: ꢀ76.92 (s, 1F). IR
ꢀ1
+
(
KBr, cm ): 3152.8, 2875.7, 2631.5; HRMS (EIꢀTOF) m/z: M Calcd for C18
67.0805.
H19ClFNO
2
S 367.0809; Found
3
1
N-(2,3-Dihydro-1H-inden-1-yl)-N-fluorobenzenesulfonamide (1s): Colorless oil, 203.7 mg, yield 70%; H NMR
(400 MHz, CDCl ) δ: 8.11ꢀ7.98 (m, 2H), 7.74 (m, 1H), 7.64ꢀ7.58 (m, 2H), 7.48ꢀ7.44 (m, 2H), 7.33ꢀ7.20 (m, 2H),
3
5
.54 (ddd, J = 39.9, 8.1, 5.5 Hz, 1H), 3.10ꢀ3.00 (m, 1H), 2.95ꢀ2.80 (m, 1H), 2.45ꢀ2.34 (m, 1H), 2.65ꢀ2.15 (m, 1H);
1
3
2
C NMR (100 MHz, CDCl
3
) δ: 144.1, 138.4, 135.2, 134.9, 129.6, 129.4, 129.0, 126.9, 125.5, 124.9, 67.7 (d, JC-F
=
3
19
ꢀ1
1
3
3.2 Hz, 1C), 31.1, 26.7 (d, JC-F = 10.3 Hz, 1C); F NMR (376 MHz, CDCl ) δ: ꢀ71.14 (s, 1F). IR (KBr, cm ):
+
3142.5, 2621.0, 2545.8; HRMS (EIꢀTOF) m/z: M Calcd for C15
H14FNO
2
S 291.0729; Found 291.0726.
1
N-(1-Phenylethyl)benzenesulfonamide (1t): White solid, 248.0 mg, yield 95%; H NMR (400 MHz, CDCl ) δ:
3
7
1
1
.76ꢀ7.69 (m, 2H), 7.51ꢀ7.46 (m, 1H), 7.40ꢀ7.35 (m, 2H), 7.19ꢀ7.15 (m, 3H), 7.08ꢀ7.05 (m, 2H), 4.97 (d, J = 6.9 Hz,
1
3
H), 4.50 (p, J = 6.9 Hz, 1H), 1.43 (d, J = 6.9 Hz, 3H); C NMR (100 MHz, CDCl
3
) δ: 141.9, 140.7, 132.5, 128.9,
28.7, 127.7, 127.1, 126.2, 53.9, 23.7.
1
N-Chloro-N-(1-phenylethyl)benzenesulfonamidee (1u): White solid, 265.5 mg, yield 90%; H NMR (400 MHz,
CDCl ) δ: 7.98ꢀ7.90 (m, 2H), 7.67ꢀ7.60 (m, 1H), 7.56ꢀ7.50 (m, 2H), 7.43ꢀ7.39 (m, 2H), 7.36ꢀ7.30 (m, 3H), 5.56 (q, J
3
1
3
=
6.7 Hz, 1H), 1.52 (d, J = 6.7 Hz, 3H); C NMR (100 MHz, CDCl
3
) δ: 138.7, 136.5, 134.0, 129.1, 128.5, 128.4,
+
1
27.91, 60.8, 16.6. HRMS (EIꢀTOF) m/z: M Calcd for C14
H14ClNO
2
S 295.0434; Found 295.0432.
1
N-Fluoro-N-(1-phenylpropan-2-yl)benzenesulfonamide (1v): Colorless oil, 190.5 mg, yield 65%; H NMR (400
MHz, CDCl
3
) δ: 7.86ꢀ7.80 (m, 2H), 7.65ꢀ7.58 (m, 1H), 7.52ꢀ7.44 (m, 2H), 7.30ꢀ7.05 (m, 5H), 4.38 (d, J = 41.1 Hz,
13
1
1
9
H), 4.37ꢀ4.12 (m, 1H), 3.16ꢀ3.07 (m, 1H), 1.19 (dd, J = 6.6, 1.2 Hz, 3H); C NMR (100 MHz, CDCl ) δ: 137.7,
3
2
3
3
35.8, 134.6, 129.5, 129.3, 128.6, 126.8, 60.5 (d, JC-F = 12.9 Hz, 1C), 40.4 (d, JC-F = 2.9 Hz, 1C), 15.6 (d, JC-F
=
19
ꢀ1
.7 Hz, 1C); F NMR (376 MHz, CDCl
3
) δ: ꢀ79.17 (s, 1F). IR (KBr, cm ): 3021.8, 2917.5, 2856.5; HRMS
+
(EIꢀTOF) m/z: M Calcd for C15
H16FNO
2
S 293.0886.; Found 293.0884.
1
N-Fluoro-N-isopropylbenzenesulfonamide (1w): Colorless oil, 141.1 mg, yield 65%; H NMR (400 MHz, CDCl
3
)
δ: 7.99ꢀ7.94 (m, 2H), 7.73ꢀ7.67 ( m, 1H), 7.67ꢀ7.54 (m, 2H), 4.12 (dp, J = 34.6, 6.5 Hz, 1H), 1.31 (dd, J = 6.6, 1.1 Hz,
13
2
3
6
H); C NMR (100 MHz, CDCl
3
) δ: 135.4, 134.6, 129.4, 129.3, 55.5 (d, JC-F = 13.4 Hz, 1C), 19.4 (d, JC-F = 6.8 Hz,
19
ꢀ1
1C); F NMR (376 MHz, CDCl
3
) δ: ꢀ75.91 (s, 1F). IR (KBr, cm ): 3002.8, 2856.3, 2813.5; HRMS (EIꢀTOF) m/z:
+
M Calcd for C
9
H12FNO
2
S 217.0573; Found 217.0569.
1
N-(4-Chlorobenzyl)-N-fluorobenzenesulfonamide (1x): Colorless oil,194.4 mg, yield 65%; H NMR (400 MHz,
1
3
CDCl ) δ: 8.05ꢀ7.99 (m, 2H), 7.85ꢀ7.75 (m, 1H), 7.70ꢀ7.60 (m, 2H), 7.35ꢀ7.25 (m, 4H), 4.38 (d, J = 41.1 Hz, 2H);
C
3
2
19
NMR (100 MHz, CDCl
3
) δ: 135.3, 134.8, 132.2, 131.1, 130.5, 130.1, 129.6, 129.1, 56.7 (d, JC-F = 13.0 Hz, 1C);
F
ꢀ
1
+
NMR (376 MHz, CDCl
3
) δ: ꢀ46.09 (s, 1F). IR (KBr, cm ): 3102.6, 2934.5, 2876.3; HRMS (EIꢀTOF) m/z: M Calcd
2
for C13H11ClFNO S 299.0183; Found 299.0179.
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N-Phenylbenzenesulfonamide (2a): White solid, 55.3 mg, yield 95%; H NMR (400 MHz, CDCl
3
) δ: 7.81ꢀ7.78 (m,
1
3
2
H), 7.55ꢀ7.51 (m, 1H), 7.45ꢀ7.41 (m, 2H), 7.25ꢀ7.21 (m, 2H), 7.14(s, 1H), 7.12ꢀ7.07 (m, 2H); C NMR (100 MHz,
CDCl ) δ: 136.5, 133.2, 129.5, 129.2, 127.4, 125.6, 121.8.
N-(p-Tolyl)benzenesulfonamide (2b): White solid, 57.4 mg, yield 93%; H NMR (400 MHz, CDCl
3
1
3
) δ: 7.79ꢀ7.77
m, 2H), 7.54ꢀ7.51 (m, 1H), 7.42ꢀ7.39 (m, 2H), 7.21 (s, 1H), 7.03ꢀ6.96 (m, 4H), 2.25 (s, 3H); C NMR (100 MHz,
CDCl ) δ: 139.1, 135.5, 133.8, 133.0, 130.0, 129.1, 127.4, 20.9.
N-(4-(tert-Butyl)phenyl)benzenesulfonamide (2c): White solid, 67.2 mg, yield 93%; H NMR (400 MHz,
DMSOꢀd ) δ: 10.20 (s, 1H), 7.77ꢀ7.75 (m, 2H), 7.62ꢀ7.52 (m, 3H), 7.24ꢀ7.22 (m, 2H), 7.02ꢀ6.98 (m, 2H), 1.18 (s,
1
3
(
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
6
13
9
H); C NMR (100 MHz, DMSOꢀd
6
) δ: 146.4, 139.8, 134.96, 132.8, 129.3, 126.6, 125.9, 119.9, 34.0, 31.1.
1
N-(4-Methoxyphenyl)benzenesulfonamide (2d): White solid, 63.8 mg, yield 97%; H NMR (400 MHz, CDCl ) δ:
3
7
2
1
.69 (d, J = 8.0 Hz, 2H), 7.54 (t, J = 7.6Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H), 6.96 (d, J = 8.4 Hz, 2H), 6.77 (d, J = 8.0 Hz,
13
H), 6.38 (s, 1H), 3.76 (s, 3H); C NMR (100 MHz, CDCl
3
) δ: 55.5, 114.6, 125.7, 127.4, 128.8, 129.1, 133.0, 139.0,
58.2.
1
N-([1,1'-Biphenyl]-2-yl)benzenesulfonamide (2f): White solid, 55.6 mg, yield 72%; H NMR (400 MHz, CDCl
3
)
1
3
δ: 7.75ꢀ7.71 (m, 1H), 7.59ꢀ7.52 (m, 3H), 7.43ꢀ7.29 (m, 6H), 7.19ꢀ7.07 (m, 2H), 6.84ꢀ6.78 (m, 2H), 6.60 (s, 1H);
C
NMR (100 MHz, CDCl
3
) δ: 139.1, 137.2, 134.3, 133.6, 133.1, 130.4, 129.2, 129.1, 128.9, 128.8, 128.2, 127.2, 125.2,
1
21.8.
1
N-(2-Bromophenyl)benzenesulfonamide (2g): White solid, 33.6 mg, yield 43%; H NMR (400 MHz, CDCl
3
) δ:
7.77ꢀ7.74 (m, 2H), 7.68 (dd, J = 8.2, 1.5 Hz, 1H), 7.57ꢀ7.52 (m, 1H), 7.46ꢀ7.39 (m, 3H), 7.31ꢀ7.26 (m, 1H),
1
3
7
1
.02ꢀ6.93 (m, 1H), 6.97 (s, 1H); C NMR (100 MHz, CDCl ) δ: 138.9, 134.7, 133.5, 132.7, 129.2, 128.8, 127.4,
3
26.6, 123.0, 116.1.
1
N-(m-Tolyl)benzenesulfonamide (2h): White solid, 60.5 mg, yield 98%; H NMR (400 MHz, DMSOꢀd
6
) δ: 10.23
1
3
(
s, 1H), 7.78ꢀ7.73 (m, 2H), 7.63ꢀ7.21 (m, 3H), 7.12ꢀ7.06 (m, 1H), 6.90 (s, 1H), 6.90ꢀ6.80 (m, 2H), 2.18(s, 3H); C
NMR (100 MHz, CDCl
3
) δ: 139.5, 139.2, 136.4, 133.1, 129.2, 129.1, 127.4, 126.4, 122.4, 118.7, 21.5.
1
N-(3,4-Dimethylphenyl)benzenesulfonamide (2i): White solid, 62.6 mg, yield 96%; H NMR (400 MHz, CDCl )
3
δ: 7.81ꢀ7.76 (m, 2H), 7.55ꢀ7.49 (m, 1H), 7.46ꢀ7.29 (m, 2H), 6.98ꢀ6.95 (m, 1H), 6.94ꢀ6.90 (s, 1H), 6.88ꢀ6.84 (m, 1H),
13
6
.81ꢀ6.77 (m, 1H), 2.16 (d, J = 2.8 Hz, 6H); C NMR (100 MHz, CDCl
3
) δ: 139.2, 137.8, 134.3, 133.9, 133.0, 130.4,
129.1, 127.4, 123.7, 119.7, 19.9, 19.3.
1
N-(Thiophen-2-yl)benzenesulfonamide (2j): White solid, 35.8 mg, yield 60%; H NMR (400 MHz, CDCl
3
) δ:
7
6
1
.81ꢀ7.73 (m, 2H), 7.62ꢀ7.55 (m, 1H), 7.51ꢀ7.43 (m, 2H), 7.02 (dd, J = 5.6, 1.4 Hz, 1H), 6.83ꢀ6.78 (m, 1H),
1
3
.72ꢀ6.68 (m, 1H), 6.60 (s, 1H); C NMR (100 MHz, CDCl
3
) δ: 138.4, 136.9, 133.4, 129.2, 127.7, 125.9, 124.2,
23.7.
1
N-(Naphthalen-2-yl)benzenesulfonamide (2k): White solid, 67.9 mg, yield 96%; H NMR (400 MHz, CDCl
3
) δ:
13
7
1
4
.83ꢀ7.70 (m, 5H), 7.52ꢀ7.31 (m, 7H), 6.86 (s, 1H); C NMR (100 MHz, CDCl
3
) δ: 139.6, 134.7, 133.4, 131.6,
29.4, 129.4, 128.9, 127.9, 127.7, 127.1, 126.8, 125.9, 123.7, 121.8.
1
3
-Nitro-N-phenylbenzenesulfonamide (2l): White solid, 66.0 mg, yield 95%; H NMR (400 MHz, CDCl ) δ:
13
8.30ꢀ8.26 (m, 2H), 7.93ꢀ7.90 (m, 2H), 7.31ꢀ7.26 (m, 2H), 7.26ꢀ7.18 (m, 2H), 7.09ꢀ7.05 (m, 2H), 6.60 (s, 1H);
NMR (100 MHz, CDCl ) δ: 150.4, 144.8, 135.4, 129.8, 128.7, 126.6, 124.4, 122.6.
C
3
1
N-(4-Methoxyphenyl)-4-nitrobenzenesulfonamide (2m): White solid, 75.47 mg, yield 98%; H NMR (400 MHz,
DMSOꢀd ) δ: 10.24 (s, 1H), 8.78ꢀ8.34 (m, 2H), 7.92ꢀ7.87 (m, 2H), 6.99ꢀ6.95 (m, 2H), 6.83ꢀ6.80 (m, 2H), 3.67 (s,
6
13
3
H); C NMR (100 MHz, DMSOꢀd
6
) δ: 156.2, 149.3, 144.1, 128.5, 127.6, 124.2, 123.4, 114.1, 55.3.
1
4-Chloro-N-phenylbenzenesulfonamide (2n): White solid, 64.8 mg, yield 97%; H NMR (400 MHz, CDCl
3
) δ:
13
7
.70ꢀ7.68 (m, 2H), 7.41ꢀ7.39 (m, 2H), 7.28ꢀ7.24 (m, 2H), 7.16ꢀ7.13 (m, 1H), 7.08ꢀ7.06 (m, 2H), 6.78 (s, 1H);
C
NMR (100 MHz, CDCl
3
) δ: 139.8, 137.5, 136.1, 129.6, 129.5, 128.8, 126.0, 122.1.
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N-(4-(tert-Butyl)phenyl)-4-chlorobenzenesulfonamide (2o): White solid, 75.1 mg, yield 93%; H NMR (400
6
MHz, DMSOꢀd ) δ: 10.52 (s, 1H), 8.39ꢀ8.35 (m, 2H), 8.01ꢀ7.98 (m, 2H), 7.28ꢀ7.24 (m, 2H), 7.04ꢀ7.00 (m, 2H), 1.19
13
(
s, 9H); C NMR (100 Hz, DMSOꢀd
6
) δ: 149.8, 147.1, 145.2, 134.2, 128.2, 126.1, 124.7, 120.5, 34.0, 31.0.
1
4
-Chloro-N-(4-fluorophenyl)benzenesulfonamide (2p): White solid, 63.4 mg, yield 89%; H NMR (400 MHz,
1
3
CDCl ) δ: 7.67ꢀ7.64 (m, 2H), 7.43ꢀ7.39 (m, 2H), 7.07ꢀ7.03 (m, 3H), 6.98ꢀ6.92 (m, 2H); C NMR (100 MHz, CDCl3)
3
δ: 162.3, 159.8, 139.9, 137.2, 131.9, 131.8, 129.6, 128.8, 125.2, 125.1, 116.6, 116.3.
0
1
2
3
4
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8
9
0
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2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
N-(2-(5-Oxopentyl)phenyl)benzenesulfonamide (2q): Yellow oil, 35.7 mg, yield 45%; H NMR (400 MHz,
CDCl
.14ꢀ7.09 (m, 3H), 6.77 (s, 1H), 2.43ꢀ2.34 (m, 3H), 1.88ꢀ1.70 (m, 1H), 1.56ꢀ1.50 (m, 2H), 1.45ꢀ1.36 (m, 2H);
NMR (100 MHz, CDCl ) δ: 202.6, 139.7, 136.1, 133.9, 133.1, 129.9, 129.1, 127.3, 127.1, 126.8, 125.3, 43.6, 30.6,
3
) δ: 9.71 (t, J = 1.7 Hz, 1H), 7.77ꢀ7.71 (m, 2H), 7.57ꢀ7.52 (m, 1H), 7.46ꢀ7.41 (m, 2H), 7.25ꢀ7.22 (m, 1H),
13
7
C
3
2
9.5, 21.8. IR (KBr, cmꢀ1): 3336.5, 3250.5, 2922.8, 1524.8, 1347.7, 1306.9, 1156.8, 982.9, 738.8; HRMS (EIꢀTOF)
+
m/z: M Calcd for C17
H
19NO
3
S 317.1086; Found 317.1091.
1
Chlorocyclohexan-1-one (2r): Colorless oil, 21.8 mg, yield 66%; H NMR (400 MHz, CDCl
3
) δ: 4.36ꢀ4.24 (m, 1H),
.85ꢀ2.80 (m, 1H), 2.55ꢀ2.51 (m, 2H), 1.70ꢀ1.69 (m, 3H), 1.59ꢀ1.50 (m, 2H); C NMR (100 MHz, CDCl ) δ: 203.6,
63.0, 42.1, 39.6, 37.6, 23.1.
13
2
3
1
2
,3-Dihydro-1H-inden-1-one (2s): White solid, 52.8 mg, yield 91%; H NMR (400 MHz, CDCl
3
) δ: 7.78ꢀ7.72 (m,
13
1
H), 7.62ꢀ7.54 (m, 1H), 7.52ꢀ7.44 (m, 1H), 7.40ꢀ7.32 (m, 1H), 3.20ꢀ3.10 (m, 2H), 2.75ꢀ2.65 (m, 2H); C NMR (100
MHz, CDCl
3
) δ: 207.3, 155.3, 137.2, 134.7, 127.4, 126.8, 123.9, 36.4, 25.9.
1
4-Chlorobenzaldehyde (2x): White solid, 28.0 mg, yield 80%; H NMR (400 MHz, CDCl
3
) δ: 9.98 (s, 1H);
1
3
7
.85ꢀ7.80 (m, 2H), 7.54ꢀ7.49 (m, 2H); C NMR (100 MHz, CDCl ) δ: 191.0, 141.1, 134.8, 131.1, 129.6.
3
1
Benzenesulfonamide (2y): White solid, 30.6 mg, yield 78%; H NMR (400 MHz, CDCl
3
) δ: 7.96ꢀ7.92 (m, 2H),
1
3
7
.63ꢀ7.59 (m, 1H); 7.58ꢀ7.59 (m, 2H), 4.87 (s, 2H); C NMR (100 MHz, CDCl
3
) δ: 142.09, 132.95, 129.31, 126.57.
ASSOCIATED CONTENT:
The Supporting Information is available free of charge on the ACS Publications website at DOI:
Screening of the reaction conditions and NMR spectra of compounds (PDF)
ACKNOWLEDGEMENTS:
This study was financially supported by the National Natural Science Foundation of China (21372077) and by
State Key Laboratory of Efficient Utilization for Low Grade Phosphate Rock and Its Associated Resources
(
WFKF2017ꢀ04).
References and Endnotes:
1
a) Beckmann, E. Isonitrosoꢀderivatives. Ber. Dtsch. Chem. Ges. 1886, 19, 988ꢀ993. b) Blatt, H. A. The
Beckmann rearrangement. Chem. Rev. 1933, 12, 215ꢀ260. c) Donaruma, L. G.; Heldt, W. Z. The Beckmann
Rearrangement. Org. React. 1960, 11, 1ꢀ156. d) Nguyen, M. T.; Raspoet, G.; Vanquickenborne, L. G. A
New Look at the Classical Beckmann Rearrangement: A Strong Case of Active Solvent Effect. J. Am.
Chem. Soc. 1997, 119, 2552ꢀ2562. e) Nubbemeyer, U. Synthesis of Mediumꢀsized Ring Lactams. Top.
Curr. Chem. 2001, 216, 125ꢀ196.
(a) Izumi, Y.; Sato, S.; Urabe, K. Vaporꢀphase Beckmann Rearrangement of Cyclohexanone Oxime over
Boriaꢀhydroxyapatite Catalyst. Chem. Lett. 1983, 10, 1649ꢀ1652. (b) Peng, J.; Deng, Y. Catalytic
Beckmann Rearrangement of Ketoximes in Ionic Liquids. Tetrahedron Lett. 2001, 42, 403ꢀ405.
Yamabe, S.; Tsuchida, N.; Yamazaki, S. Is the Beckmann Rearrangement a Concerted or Stepwise
Reaction? A Computational Study. J. Org. Chem. 2005, 70, 10638ꢀ10644.
2
3
4
Xie, F.; Du, C.; Pang, Y.; Lian, X.; Xue, C.; Chen, Y.; Wang, X.; Cheng, M.; Guo, C.; Lin, B.; Liu, Y.
Lewis Acidꢀassisted
NꢀFluorobenzenesulfonimideꢀbased Electrophilic Fluorine Catalysis in Beckmann
Rearrangement. Tetrahedron Lett. 2016, 57, 5820ꢀ5824.
5
(a) Differding, E.; Rüegg, G. M. Nucleophilic Substitution Versus Electron Transfer: 1. The Mechanism of
Electrophilic Fluorinations. Tetrahedron Lett. 1991, 32, 3815ꢀ3818. (b) Stavber, S.; Zupan, M. Selectfluor
FꢀTEDAꢀBF4 as a versatile mediator or catalyst in organic chemistry. Acta Chim. Slov. 2005, 52, 13ꢀ26. (c)
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Nyffeler, P. T.; Durón, S. G.; Burkart, M. D.; Vincent, S. P.; Wong, C. H. Selectfluor: Mechanistic Insight
and Applications. Angew. Chem. Int. Ed. 2005, 44, 192ꢀ212.
(a) Avril, N.; Rosé, C. A.; Schelling, M.; Dose, J.; Kuhn, W.; Bense, S.; Weber, W.; Ziegler, S.; Graeff, H.;
Schwaiger, M. Breast Imaging with Positron Emission Tomography and Fluorineꢀ18 Fluorodeoxyglucose:
Use and Limitations. J. Clin. Oncol. 2000, 18(20), 3495ꢀ3502. (b) Bobbio, C.; Gouverneur, V. Catalytic
6
7
Asymmetric Fluorinations. Org. Biomol. Chem. 2006,
Fernandez, R.; Alvarez, E.; Lassaletta, J. Enantioselective Synthesis of Vicinal Halohydrins via Dynamic
Kinetic Resolution. Org. Lett. 2006, , 127ꢀ130. (d) Arai, S.; Oku, M.; Ishida, T.; Shioiri, T. Asymmetric
Alkylation Reaction of αꢀFluorotetralone under Phaseꢀtransfer Catalyzed Conditions. Tetrahedron Lett.
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